This paper describes the study of Auger and core‐level energy shifts measured for pure Si, Ti, and TiSi2by Auger electron spectroscopy (AES), slow electron energy‐loss spectroscopy (SEELS), and internal x‐ray photoelectron spectroscopy (IXPS). The Auger line‐shape changes in TiSi2are noted and the chemical shifts measured. The deep‐core‐level loss energies of the siliconK‐ andL‐shell electron and the titaniumL‐ andM‐shell electrons are determined using SEELS technique. The collective surface and bulk plasma excitations in Ti, Si, and TiSi2are also observed. Using a high‐energy beam Si(Kα) x rays are generated to produce titanium photoelectrons by the IXPSL‐shell electrons in TiSi2. The core level shifts observed from AES, SEELS, and IXPS are compared and this confirms the already established metallic nature of the silicide.